5.

33 Lecture Notes: Introduction To Polymer Chemistry

Polymer:

A large molecule (macromolecule) built up by repetitive bonding (covalent) of smaller molecules (monomers)

Generally not a well defined structure, or molecular weight. Need to use statistical properties to describe.

Polymers are formed by linking monomers through chemical reactioncalled polymerization. You dont end up with a unique molecule.

i monomers iA

chain of monomers (AAA)i/3

Homopolymer: all A identical

The most produced/used polymers are homopolymers of terminal alkenes. Produced by radical polymerization.

i CH2=CH2
ethylene

(CH2CH2)i
polyethylene

i H2C=C

CH3 COOCH3

CH3 H2C-C
i

COOCH3
PMMA

methylmethacrylate

Copolymers:
made up of different monomers i A + i B (A-B)i

i H2C=CHCl + i H2C=CCl2
vinyl chloride vinylidene chloride

Cl

Cl
i

H2 C-CH-CH2 -C Cl

poly(vinylchloride-co-vinylidene chloride) Saran

A-B-A-B-A-B A-A-A-A-B-A-B

alternating copolymer random copolymer

Both of these are rare. Most common is a statistical copolymer, which has a statistical distribution of repeat units.

Block copolymersTwo long sequences of repeat units

A-A-A-A-A-A-A-B-B-B-B-B-B-B

AB diblock copolymer

AB graft copolymer

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Structural characteristics Closely related to material properties

linear (uninterrupted straight chain)

branched (occasional branches off longer chain)

branch point

networked (many interconnected linear chains; one giant molecule)

crosslink

Stereochemistry of Linkages
R HR HR HR H

ISOTACTIC R groups on same side of backbone

HH

RR

HH

SYNDIOTACTIC R groups on alternating sides of backbone

ATACTIC Random (most common)

Ziegler-Natta catalysts used for iso- and syndio-

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Classification of polymers:

Polymers (synthetic)
1) Thermoplastics (plastics) linear, some cross-linking can be melted and reformed on heating a) Amorphousno ordered structure b) Semi-crystallinecomposed of microscopic crystallites domains of crystalline structure. Can be ordered. Fibers (nylon, polyester)

2)

Elastomers (rubbers) moderately cross-linked can be stretched and rapidly recover their original dimension

3)

Thermostats(resins)massively cross-linked very rigid; degrade on heating

4)

Dendrimersmultiply branchedmultiple consecutive (regular) branches

Biopolymers
polypeptidesproteins-amino acid heteropolymer nucleic acidsRNA/DNA polysaccharidessugars

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Characterization 1) How do polymers respond to an applied force?

(study of flow and deformation: rheology)
viscoelastic medium

An elastic medium is described by Newtons Law: F = k x

F
x

If you apply a force (a stress), the material displaces by an amount x: x= F k

ksmall kbig F

small k: weak spring easily displaced big K: stiff spring difficult to displace

Polymers are often non-Newtonian

F
For polymers, we apply a stress, and it leads to internal distortion strain.

stress

m
elastic modulus

strain displacement

strain shear

small m stretches easily/compresses easily (rubber) large m small strain produced by stress (hard plasticsPMMA)

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The elastic modulus m is highly temperature dependent! Rubber has small m at room temperature ball bounces At low T, m much larger rubber ball in liquid N2 shatters when bounced hard plastic Also, plastics heated above room temperature are less stiff.

TYPICAL PLOT OF m(T)

log m

plastic rubber

Tmelt Tdegradation
resin

T g

Where is room temperature on this plot? (depends on whether you have a rubber or plastic) The various temperatures characterize polymers.

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2)

Molecular Weight Molar Mass (M)

i: degree of polymerization Mi = i M0 (# of monomer units) Mi : molar mass of polymer molecule i M0 : molecular weight of monomer

Typically have distribution of masses (all chain lengths arent equally long) monodisperseequal chain lengths polydisperseunequal lengths Characterize the polydispersity through F(Mi): distribution of molar masses. purified proteins, dendriners

F(Mi)

Mn
Mw

Mv

Mi
We can find several statistical ways of describing the molar mass. Comparison of these numbers helps describe F(M).

A) Number-average molar mass, M n

Mn

N M = N
i i i i

M F ( M ) dM
0

F ( M ) dM

(first moment)

Ni: # of molecules with degree of polymerization i Mi: molar mass for degree of polymerization I

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B) Mass- or Weight-average molar mass, M w M w = wi M i

i

wi is the weight fraction: the total mass of molecules with mass Mi divided by the total mass of all molecules wi = NiM i NiM i
i 2 i

Mw

N M = N M
i i i i

F ( M ) M dM F ( M ) M dM
2 0 0

(second moment of M.M.)

C) In experiment 4, we are studying viscosity-average molar mass, M v

(M ) =
a v

M 1+ a F ( M ) dM

F ( M ) dM

PolydispersityWe can describe the polydispersity through the width of the distribution of molar masses.

Mn < Mv < Mw
Mw 1 Mn
perfectly monodisperse = 1

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3)

Chain dimensions
Contour length: length along backbone n bonds of length l n l End-to-end distance: More common - measure of the coiled system The distribution of r is characterized by the rms end-to-end

distance

r2

For a freely jointed chain with n links and no restrictions on bond angle: r2 = n l Radius of gyration, Rg Rg is the rms distance of a chain segment from the center of mass of the polymer.

intrinsic viscosity

Rg =

r2 6 Rg
3

[ ]

Define a center of mass; then each chain segment has a certain distance from the center of mass

M
average x2 to get Rg

x2

= Rg

c.o.m.

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